CN108727780A - The copper-clad plate of resin combination and its making - Google Patents
The copper-clad plate of resin combination and its making Download PDFInfo
- Publication number
- CN108727780A CN108727780A CN201810413636.7A CN201810413636A CN108727780A CN 108727780 A CN108727780 A CN 108727780A CN 201810413636 A CN201810413636 A CN 201810413636A CN 108727780 A CN108727780 A CN 108727780A
- Authority
- CN
- China
- Prior art keywords
- resin
- parts
- epoxy resin
- resin combination
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 88
- 239000011347 resin Substances 0.000 title claims abstract description 88
- 239000003822 epoxy resin Substances 0.000 claims abstract description 81
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 81
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 34
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 34
- 230000000694 effects Effects 0.000 claims abstract description 30
- 229920001400 block copolymer Polymers 0.000 claims abstract description 26
- 239000013034 phenoxy resin Substances 0.000 claims abstract description 10
- 229920006287 phenoxy resin Polymers 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 35
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 35
- -1 benzene sulfone Chemical class 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 31
- 239000011889 copper foil Substances 0.000 claims description 30
- 239000004744 fabric Substances 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- 239000011574 phosphorus Substances 0.000 claims description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 15
- 229920001187 thermosetting polymer Polymers 0.000 claims description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 9
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 9
- 229940106691 bisphenol a Drugs 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 150000002460 imidazoles Chemical group 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 229920000428 triblock copolymer Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- INKDAKMSOSCDGL-UHFFFAOYSA-N [O].OC1=CC=CC=C1 Chemical compound [O].OC1=CC=CC=C1 INKDAKMSOSCDGL-UHFFFAOYSA-N 0.000 abstract description 19
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 239000003292 glue Substances 0.000 description 28
- 239000007787 solid Substances 0.000 description 26
- 239000002904 solvent Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 21
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 19
- 238000005452 bending Methods 0.000 description 18
- 238000007711 solidification Methods 0.000 description 18
- 230000008023 solidification Effects 0.000 description 18
- 150000001412 amines Chemical class 0.000 description 17
- 238000001514 detection method Methods 0.000 description 13
- 238000007654 immersion Methods 0.000 description 13
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 11
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical group CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
- B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2481/06—Polysulfones; Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to a kind of resin combination and its copper-clad plates of making.The present invention resin combination include：The epoxy resin of 100 parts by weight, the activity poly ether sulfone of 20-100 parts by weight, 5-80 parts by weight phenoxy resin and 5-40 parts by weight block copolymer.There is good deflection curvature performance, while the feature that high-fire resistance, high Tg, high heat decomposition temperature, halogen-free flame-retardance are excellent using activity poly ether sulfone, phenol oxygen, block copolymer coordination plasticizing, the semi-flexible copper-clad plate of making in the resin combination of the present invention.
Description
Technical field
The present invention relates to technical field of electronic products, more particularly to a kind of resin combination for printed circuit board and its
The copper-clad plate of making.
Background technology
With electronic product microminaturization, multifunction, it is desirable that printed circuit board (PCB) realizes densification, high-performance
Change.Under this trend, flex plate, Rigid-flex PCB can realize intensive assembling and three-dimensional assembling, hence it is evident that reduce shared by electronic product
Volume.The reinforcing material that flexibility coat copper plate (FCCL) uses at present is polyimides (PI) film, flex section in Rigid-flex PCB
The reinforcing material used is also PI films.PI films have splendid flexural property but with high costs, this leads to its derivative PCB product
Price it is also very high, and some deflection requirements are relatively low or the occasion of static bending, semi-flexible copper-clad plate, that is, alternative FCCL is full
Sufficient flexural property requirement, while reducing material cost；Semi-flexible copper-clad plate in some scenarios then may replace Rigid-flex PCB,
It saves pressing plate and engraves the flow of plate, save process cost.
Invention content
The inventors of the present application found that when using epoxy glass copper-clad plate, it is obviously high that flexure bending performance can be obtained
Go out the semi-flexible copper-clad plate of common copper-clad plate, but copper-clad plate flexure bending performance purpose is promoted to reach introducing toughened resin
While, it is possible to existing reduces the negative effect of the performances such as plank glass transition temperature (Tg), heat resistance.
For this purpose, a kind of resin combination with high glass-transition temperature (Tg), high-fire resistance of present invention offer, and by
Its semi-flexible copper-clad plate made.
One aspect of the present invention provides a kind of resin combination, including：Epoxy resin, the 20-100 weights of 100 parts by weight
The block copolymer of the activity poly ether sulfone of amount part, the phenoxy resin and 5-40 parts by weight of 5-80 parts by weight.
In certain embodiments, the epoxy resin is bisphenol A type epoxy resin, phosphorous epoxy resin, biphenyl type ring
Oxygen resin, cycloaliphatic epoxy resin are combined without one or more of brominated eopxy resin.
In certain embodiments, the activity poly ether sulfone has following structure：
Wherein, R1And R2Indicate active end group, R1And R2Can be identical or different, it is each independently selected from by hydroxyl, amido
With the group of allyl composition；The integer that n is 5~500；
When the active terminal hydroxy group of the activity poly ether sulfone, the content range of reactive hydroxyl end group is 10-500 μ eq/g.
In certain embodiments, the phenoxy resin has following structure：
Wherein, n=50~150, R1 and R2 can be identical or different, represent H atom, Br atoms each independently or contain P
The group of element.
In certain embodiments, the molecular weight of the block copolymer is 40,000-15 ten thousand, to be selected from polymethylacrylic acid
The triblock copolymer of the block structure unit of methyl esters (PMMA), butadiene and styrene.
In certain embodiments, the resin combination also includes curing agent and optional curing accelerator.
In certain embodiments, the curing agent is dicyandiamide, 4,4 '-diaminodiphenylsulfones, phosphorus-containing phenolic aldehyde, bisphenol-A
The combination of one or more of phenolic aldehyde, phenol type phenolic aldehyde, amino equivalent or the equivalent proportion of hydroxyl equivalent and epoxide equivalent are 1:1
~2；The curing accelerator is imidazoles curing accelerator.
In certain embodiments, the resin combination also includes solvent, and the solvent is dimethylacetylamide
(DMAC), the mixture of one or more of butanone (MEK), acetone, cyclohexanone, toluene solvant.
Another aspect of the present invention provides a kind of copper-clad plate, including copper foil and the thermosetting property tree that is attached on the copper foil
Oil/fat composition impregnates base fabric, wherein the compositions of thermosetting resin is above-mentioned compositions of thermosetting resin.
In certain embodiments, the copper foil be electrolytic copper foil or rolled copper foil, and/or, the base fabric be glass fibers
Tie up cloth or non-woven fabrics.
In certain embodiments, the resin coated copper foil is used for high-density interconnected printed circuit board.
It is partly scratched using activity poly ether sulfone, phenol oxygen, block copolymer coordination plasticizing, making in the resin combination of the present invention
Property copper-clad plate there is good flexure bending performance, while high-fire resistance, high Tg, high heat decomposition temperature, halogen-free flame-retardance are excellent
The characteristics of.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.
One aspect of the present invention is related to resin combination, the resin combination include epoxy resin, activity poly ether sulfone,
Phenoxy resin and block copolymer can also include following optional components：Curing agent, curing accelerator, solvent, other additions
Agent.Each component of the resin combination of the present invention described in detail below.
Epoxy resin-
Epoxy resin is one of the key component of resin combination of the present invention as matrix resin.To the ring of the present invention
Oxygen resin is not particularly limited, organic compound that can be containing at least two epoxy groups in molecular structure, for example,
Bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac type epoxy resin, cresol novolak type epoxy tree can be selected from
Fat, bisphenol-A phenolic type epoxy resin, tetramethyl bisphenol f type epoxy resin, bis-phenol M types epoxy resin, bisphenol-s epoxy resin,
Bisphenol E-type epoxy resin, bis-phenol p-type epoxy resin, trifunctional phenol-type epoxy resin, tetrafunctional phenol-type epoxy resin, naphthalene type ring
Oxygen resin, naphthol type epoxy resin, naphthol novolac type epoxy resin, anthracene type epoxy resin, phenolphthalein type epoxy resin, phenoxy group type
It is epoxy resin, norbornene-type epoxy resin, adamantane type epoxy resin, fluorenes type epoxy resin, biphenyl type epoxy resin, bicyclic
Pentadiene type epoxy resin, dicyclopentadiene phenolic aldehyde type ring oxygen resin, aralkyl-type epoxy resin, aralkyl phenolic epoxy tree
Epoxy resin, cycloaliphatic epoxy resin, polyol type epoxy resin, siliceous epoxy containing arylene ether structure in fat, molecule
Resin, nitrogen-containing epoxy thermoset, glycidyl amine epoxy resin, ethylene oxidic ester epoxy resin and importing phosphatization conjunction into these
The phosphorous epoxy resin etc. of object.
Preferably, epoxy resin can be bisphenol A type epoxy resin, phosphorous epoxy resin, biphenyl type epoxy resin, alicyclic ring
Race's epoxy resin is combined without one or more of brominated eopxy resin.
Phosphorous epoxy resin refers to the epoxy resin that phosphorus atoms are absorbed using reactive phosphorus compound, by chemical bond.Instead
The example of answering property phosphorus compound may include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5- dihydroxyphenyls
Base) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides etc..Commercially available phosphorous epoxy resin includes XZ92530 (Tao Shiization
Company), YEP-250, YEP-300 (Guang Shan Chemical Co., Ltd.s) etc..
Activity poly ether sulfone-
Activity poly ether sulfone refers to the polyether sulfone of active end group, and the example of active end group includes but not limited to hydroxyl, amine
Base, allyl and epoxy group etc..
The activity poly ether sulfone of the present invention can have following structure formula：
Wherein, R1And R2Indicate active end group, R1And R2Can be identical or different, it is each independently selected from by hydroxyl, amido
With the group of allyl composition；The integer that n is 5~500.
The molecular weight of activity poly ether sulfone can be within the scope of 1000-100000, within this range, and activity poly ether sulfone can be molten
In solvent, be easy to mix and react with epoxy resin etc., and there is no by molecular weight it is too small caused by embrittlement problem (toughness
It is low).
The active end group of activity poly ether sulfone can be preferably hydroxyl, because can greatly improve affine with epoxy resin
Property.When the active terminal hydroxy group of polyether sulfone, the content range of reactive hydroxyl end group can be 10-500 μ eq/g, preferably 100-500
μeq/g。
In the resin combination of the present invention, relative to the epoxy resin of 100 parts by weight, the dosage of activity poly ether sulfone can be with
For 20-100 parts by weight.Preferably, activity poly ether sulfone and the weight ratio of epoxy resin can be 1：1~4.5.
Phenoxy resin-
The phenoxy resin of resin combination for the present invention can have following structure：
Wherein, n=50~150, R1 and R2 can be identical or different, represent H atom, Br atoms each independently or contain P
Element (such as DOPO, etc.).
In the resin combination of the present invention, relative to the epoxy resin of 100 parts by weight, the dosage of phenoxy resin can be
10-20 parts by weight.In addition, phenoxy resin and the amount ratio of activity poly ether sulfone can be 1：1~10, preferably 1：2~4.
In the resin combination of the present invention, phenoxy resin and activity poly ether sulfone have toughening effect to epoxy resin,
Sometimes the two may be collectively referred to as toughened resin.
Block copolymer-
Block copolymer for the present invention can be selected from polymethyl methacrylate (PMMA), polybutadiene and polyphenyl
The triblock copolymer of the block structure unit of ethylene, molecular weight ranges are 40,000-15 ten thousand, polymethyl methacrylate
(PMMA) molar content 20%~50%, polybutadiene molar content 30%~60% and polystyrene molar content 30%~
50%.
In the present invention, relative to the epoxy resin of 100 parts by weight, the dosage of block copolymer can be 5-40 parts by weight
Preferably, the dosage of block copolymer can be between epoxy resin and the 2%~15% of toughened resin total amount.
Curing agent-
It can contain curing agent in the resin combination of the present invention.Curing agent can be selected from the solidification for epoxy resin
Agent.In the present invention, it is preferred to amine curing agent (such as fatty amine, aromatic amine) and phenolic resin curing agent.For example, curing agent can
Think the group of one or more of dicyandiamide, 4,4' diaminodiphenyl sulfone, phosphorus-containing phenolic aldehyde, bisphenol-A phenolic, phenol type phenolic aldehyde
It closes.
Curing agent is appropriate in the present invention, and making its equivalent proportion with epoxy resin, (amino equivalent or hydroxyl equivalent are worked as with epoxy
The equivalent proportion of amount) can be 1:1~2.
Curing accelerator-
It can also contain curing accelerator in the resin combination of the present invention.It is solid for being used as using amine or phenolic resin
For the epoxy systems of agent, curing accelerator is preferably glyoxaline compound, such as imidazoles (2-methylimidazole, 1- methyl miaows
Azoles) etc. and its derivative.
Relative to the epoxy resin (matrix resin) of 100 parts by weight, the dosage of curing accelerator can be 0.1~2 weight
Part, to play the role of adjusting resin combination gelation index, ensure that technology controlling and process is stablized.
Solvent-
Solvent can be contained in the resin combination of the present invention, by above-mentioned epoxy resin, toughened resin, curing agent etc.
Dissolving forms glue together.Preferably, solvent can be dimethylacetylamide (DMAC), butanone (MEK), acetone, cyclohexanone, first
The mixture of one or more of benzene solvent.Mixed solvent can be for example, the two in above-mentioned solvent or three kinds with 1 ︰ 1 or
The mixed solvent of 1 ︰, 1 ︰ 1 mixing.
In the present invention, the dosage of solvent is appropriate, has the viscosity (such as 300-600cPas) convenient for coating to be formed
Glue.For example, the solid content in glue can be 40 weight %-60 weight %.
Other additives-
In the range of not losing the effect of the present invention, resin combination of the invention can also include that filler is (organic to fill out
Material and inorganic filler) or auxiliary agent etc., such as fire retardant, levelling agent, colorant, dispersant, coupling agent, foaming agent etc..
Another aspect of the present invention is related to a kind of semi-flexible copper-clad plate and preparation method thereof.
The semi-flexible copper-clad plate of the present invention includes copper foil and the compositions of thermosetting resin being attached on copper foil dipping
Base fabric, wherein compositions of thermosetting resin are above-mentioned compositions of thermosetting resin.
Copper foil can be electrolytic copper foil or rolled copper foil.
Base fabric can be glass fabric or non-woven fabrics.
The semi-flexible copper-clad plate of the present invention can make by the following method：
Resin combination each component is dissolved into glue together by solvent, it is then that base fabric (such as glass fabric) is equal
Even infiltration glue toasts 5-10 minutes in 110-160 DEG C of baking oven, makes resin combination semi-solid preparation (forming prepreg), so
It presses solidification together with copper foil (such as 1/2OZ copper foils) afterwards, semi-flexible copper-clad plate is made.
Pressing solidification can carry out under the following conditions：The prepreg cut is laminated on copper foil, with 1-3 DEG C/
The heating rate progress hot pressing of min, pressure maximum 300-500PSI, and in maximum temperature
180-200 DEG C keeps 30-120 minutes (such as 60-120 minutes).
It in certain embodiments, can be by copper-clad plate punch forming in punch die of the present invention.Preferably, the temperature of punching press
It spends within the scope of ± 30 DEG C of the Tg values for being chosen at copper-clad plate (compositions of thermosetting resin).
Due to using activity poly ether sulfone, phenol oxygen, block copolymer coordination plasticizing in the resin combination of the present invention, making
Semi-flexible copper-clad plate has good flexure bending performance, while high-fire resistance, high Tg, high heat decomposition temperature, halogen-free flame-retardance
Excellent feature.
Embodiment
The technical solution further illustrated the present invention below by embodiment, but these embodiments are not in any way
It limits the scope of the invention.
In the examples below, unless otherwise noted, the mass parts of organic resin are based on organic solid quality part.
Embodiment one：
Resin combination includes：100 parts of epoxy resin (Nippon Steel, TX1467), hydroxyl polyether sulfone (SOLVAY,
3600RP, molecular weight are 4 ten thousand) 30 parts, 12.5 parts of phenol oxygen (Inchem, PKHH, hydroxyl), block copolymer (Arkema, E21)
20 parts, 15 parts of phosphorus-containing phenolic aldehyde (DOW, XZ92741), 5 parts of amine (dicyandiamide).0.2 part of imidazoles is added in the composition
Accelerating agent and appropriate solvent (DMAC：MEK=1:1), control solid content is 40% -50%, you can is made into glue, is stirred
By glass-fiber-fabric homogeneous immersion glue after uniformly, after in an oven 155 degree toast 7 minutes, make resin combination semi-solid preparation, then with
At 190 DEG C, pressing cures 60 minutes 18u rolled copper foils together, and semi-flexible copper-clad plate is made.Detection performance is shown in Table 1.
Embodiment two：
Resin combination includes：100 parts of epoxy resin (Guangdong Guang Shan, YEP-300D, phosphorous epoxy resin), hydroxyl are poly-
(SOLVAY, 3000RP, molecular weight are 7 ten thousand) 66 parts to ether sulfone, 26 parts of phenol oxygen (Inchem, PKHH, hydroxyl), block copolymer
20 parts of (Arkema, M22N), 20 parts of phosphorus-containing phenolic aldehyde (DOW, XZ92741), 5 parts of amine (dicyandiamide).Add again in the composition
Enter 0.5 part of Imidizole accelerator and appropriate solvent (DMAC：MEK=1:1), control solid content is 40% -60%, you can is made into
Glue, by glass-fiber-fabric homogeneous immersion glue after being uniformly mixed, after in an oven 155 degree toast 7 minutes, make resin combination
Then semi-solid preparation presses solidification (condition is with embodiment 1) together with 18u rolled copper foils, semi-flexible copper-clad plate is made.Detection performance
It is shown in Table 1.
Embodiment three：
Resin combination includes：100 parts of epoxy resin (stepping figure, EPIKOTE 1001), hydroxyl polyether sulfone (SOLVAY,
3000RP, ten thousand) 50 parts of molecular weight 7,20 parts of phenol oxygen (Nippon Steel, ERF-001, group containing P), block copolymer (Arkema,
M52N) 20 parts, 20 parts of phosphorus-containing phenolic aldehyde (DOW, XZ92741), 5 parts of amine curing agent (dicyandiamide).It adds in the composition
0.1 part of Imidizole accelerator and appropriate solvent (DMAC：MEK=1:1), control solid content is 40% -60%, you can matches plastic
Liquid, by glass-fiber-fabric homogeneous immersion glue after being uniformly mixed, after in an oven 155 degree toast 7 minutes, make resin combination half
Solidification, then presses solidification (condition is with embodiment 1) together with 18u rolled copper foils, and semi-flexible copper-clad plate is made.Detection performance is shown in
Table 1.
Comparative example one：
Resin combination includes：100 parts of epoxy resin (Guangdong Guang Shan, YEP-300D), (Inchem, PKHH contain hydroxyl to phenol oxygen
Base) 30 parts, 20 parts of phosphorus-containing phenolic aldehyde (DOW, XZ92741), 7.5 parts of amine (dicyandiamide).0.2 part is added in the composition
Imidizole accelerator and appropriate solvent (DMAC：MEK=1:1), control solid content is 40% -60%, you can is made into glue, stirs
After mixing by glass-fiber-fabric homogeneous immersion glue, after in an oven 155 degree toast 7 minutes, make resin combination semi-solid preparation, so
It presses solidification (condition is with embodiment 1) together with 18u rolled copper foils afterwards, semi-flexible copper-clad plate is made.Detection performance is shown in Table 1.
Comparative example two
Resin combination includes：100 parts of epoxy resin (Guangdong Guang Shan, YEP-300D), (Inchem, PKHH contain hydroxyl to phenol oxygen
Base) 25 parts, block copolymer (Arkema, M22N, acrylic acid (PMMA) content 30% -33.5%, nitrile rubber content
35% -38% and styrene-content 35% -37.3%) 10 parts, 20 parts of phosphorus-containing phenolic aldehyde (DOW, XZ92741), amine (double cyanogen
Amine) 5 parts.0.1 part of Imidizole accelerator and appropriate solvent (DMAC are added in the composition：MEK=1:1), control contains admittedly
Amount is 40% -60%, you can be made into glue, by glass-fiber-fabric homogeneous immersion glue after being uniformly mixed, after in an oven 155
Degree baking 7 minutes, makes resin combination semi-solid preparation, then presses solidification (condition is with embodiment 1) together with 18u rolled copper foils,
Semi-flexible copper-clad plate is made.Detection performance is shown in Table 1.
Comparative example three：
Resin combination includes：100 parts of epoxy resin (Guangdong Guang Shan, YEP-300D), hydroxyl polyether sulfone (SOLVAY,
3000RP, ten thousand) 40 parts of molecular weight 7,20 parts of phenol oxygen (Inchem, PKHH, hydroxyl), 15 parts of phosphorus-containing phenolic aldehyde (DOW, XZ92741),
5 parts of amine (dicyandiamide).0.5 Imidizole accelerator and appropriate solvent (DMAC are added in the composition：MEK=1:1) it, controls
Solid content processed is 40% -60%, you can be made into glue, by glass-fiber-fabric homogeneous immersion glue after being uniformly mixed, after in baking oven
In 155 degree toast 7 minutes, make resin combination semi-solid preparation, then pressed together with 18u rolled copper foils solidification (condition with implementation
Example 1), semi-flexible copper-clad plate is made.Detection performance is shown in Table 1.
Comparative example four：
Resin combination includes：100 parts of epoxy resin (Guangdong Guang Shan, YEP-300D), hydroxyl polyether sulfone (SOLVAY,
3000RP, ten thousand) 40 parts of molecular weight 7, block copolymer (Arkema, M22N, acrylic acid (PMMA) content 30% -33.5%, fourth
Nitrile rubber content 35% -38% and styrene-content 35% -37.3%) 20 parts, 15 parts of phosphorus-containing phenolic aldehyde (DOW, XZ92741),
5 parts of amine (dicyandiamide).0.2 part of Imidizole accelerator and appropriate solvent (DMAC are added in the composition：MEK=1:1),
Solid content is controlled 40% -60%, you can be made into glue, by glass-fiber-fabric homogeneous immersion glue after being uniformly mixed, after drying
It is toasted 7 minutes for 155 degree in case, makes resin combination semi-solid preparation, then pressing solidification together with 18u rolled copper foils, (condition is the same as real
Apply example 1), semi-flexible copper-clad plate is made.Detection performance is shown in Table 1.
Comparative example five：
Resin combination includes：65 parts of epoxy resin (Guangdong Guang Shan, YEP-300D), hydroxyl polyether sulfone (SOLVAY,
3000RP, ten thousand) 10 parts of molecular weight 7,20 parts of phenol oxygen (Inchem, PKHH, hydroxyl), block copolymer (Arkema, M52N) 20
Part, 25 parts of phosphorus-containing phenolic aldehyde (DOW, XZ92741), 7.5 parts of amine (dicyandiamide).0.2 part of imidazoles is added in the composition
Accelerating agent and appropriate solvent (DMAC：MEK=1:1), control solid content is 40% -50%, you can is made into glue, is stirred
By glass-fiber-fabric homogeneous immersion glue after uniformly, after in an oven 155 degree toast 7 minutes, make resin combination semi-solid preparation, then with
18u rolled copper foils press solidification (condition is with embodiment 1) together, and semi-flexible copper-clad plate is made.Detection performance is shown in Table 1.
Comparative example six：
Resin combination includes：100 parts of epoxy resin (Guangdong Guang Shan, YEP-300D), hydroxyl polyether sulfone (SOLVAY,
3000RP, ten thousand) 110 parts of molecular weight 7,30 parts of phenol oxygen (Inchem, PKHH), 20 parts of block copolymer (Arkema, M22N) are phosphorous
10 parts of phenolic aldehyde (DOW, XZ92741), 5 parts of amine (dicyandiamide).1 part of Imidizole accelerator and appropriate is added in the composition
Solvent (DMAC：MEK=1:1), control solid content is 40% -60%, you can glue is made into, by glass after being uniformly mixed
Cloth homogeneous immersion glue, after in an oven 155 degree toast 7 minutes, make resin combination semi-solid preparation, then with 18u rolled copper foils
Semi-flexible copper-clad plate is made in pressing solidification (condition is with embodiment 1) together.Detection performance is shown in Table 1.
Comparative example seven：
Resin combination includes：100 parts of epoxy resin (Guangdong Guang Shan, YEP-300D, phosphorous epoxy resin), hydroxyl are poly-
66 parts of ether sulfone (SOLVAY, 3000RP), 26 parts of phenol oxygen (Inchem, PKHH, hydroxyl), block copolymer (Arkema, M22N)
20 parts, 20 parts of phosphorus-containing phenolic aldehyde (DOW, XZ92741), 2 parts of amine (dicyandiamide), the total amount and epoxy of amino equivalent and hydroxyl equivalent
The equivalent proportion of equivalent is less than 0.5.0.2 part of Imidizole accelerator and appropriate solvent (DMAC are added in the composition：MEK=
1:1), control solid content is 40% -50%, you can it is made into glue, by glass-fiber-fabric homogeneous immersion glue after being uniformly mixed,
Afterwards in an oven 155 degree toast 7 minutes, make resin combination semi-solid preparation, then press solidification (item together with 18u rolled copper foils
Part is with embodiment 1), semi-flexible copper-clad plate is made.Detection performance is shown in Table 1.
Comparative example eight：
Resin combination includes：100 parts of epoxy resin (Guangdong Guang Shan, YEP-300D, phosphorous epoxy resin), hydroxyl are poly-
66 parts of ether sulfone (SOLVAY, 3000RP), 26 parts of phenol oxygen (Inchem, PKHH, hydroxyl), block copolymer (Arkema, M22N)
20 parts, 20 parts of phosphorus-containing phenolic aldehyde (DOW, XZ92741), 10 parts of amine (dicyandiamide), the total amount and ring of amino equivalent and hydroxyl equivalent
The equivalent proportion of oxygen equivalent is more than 1.0.2 part of Imidizole accelerator and appropriate solvent (DMAC are added in the composition：MEK=
1:1), control solid content is 40% -50%, you can it is made into glue, by glass-fiber-fabric homogeneous immersion glue after being uniformly mixed,
Afterwards in an oven 155 degree toast 7 minutes, make resin combination semi-solid preparation, then press solidification (item together with 18u rolled copper foils
Part is with embodiment 1), semi-flexible copper-clad plate is made.Detection performance is shown in Table 1.
Comparative example nine：
Resin combination includes：100 parts of epoxy resin (stepping figure, EPIKOTE 1001), hydroxyl polyether sulfone (SOLVAY,
3000RP, ten thousand) 50 parts of molecular weight 7,20 parts of phenol oxygen (Nippon Steel, ERF-001, group containing P), block copolymer (Arkema,
M52N) 4.5 parts, 20 parts of phosphorus-containing phenolic aldehyde (DOW, XZ92741), 5 parts of amine curing agent (dicyandiamide).It adds in the composition
0.1 part of Imidizole accelerator and appropriate solvent (DMAC：MEK=1:1), control solid content is 40% -60%, you can matches plastic
Liquid, by glass-fiber-fabric homogeneous immersion glue after being uniformly mixed, after in an oven 155 degree toast 7 minutes, make resin combination half
Solidification, then presses solidification (condition is with embodiment 1) together with 18u rolled copper foils, and semi-flexible copper-clad plate is made.Detection performance is shown in
Table 1.
Comparative example ten：
Resin combination includes：100 parts of epoxy resin (stepping figure, EPIKOTE 1001), hydroxyl polyether sulfone (SOLVAY,
3000RP, ten thousand) 50 parts of molecular weight 7,20 parts of phenol oxygen (Nippon Steel, ERF-001, group containing P), block copolymer (Arkema,
M52N) 100 parts, 20 parts of phosphorus-containing phenolic aldehyde (DOW, XZ92741), 5 parts of amine curing agent (dicyandiamide).It adds in the composition
0.1 part of Imidizole accelerator and appropriate solvent (DMAC：MEK=1:1), control solid content is 40% -60%, you can matches plastic
Liquid, by glass-fiber-fabric homogeneous immersion glue after being uniformly mixed, after in an oven 155 degree toast 7 minutes, make resin combination half
Solidification, then presses solidification (condition is with embodiment 1) together with 18u rolled copper foils, and semi-flexible copper-clad plate is made.Detection performance is shown in
Table 1.
The test method of the above characteristic is as follows：
(1) glass transition temperature (Tg)：It is tested using DMA (Dynamic thermomechanical analysis),
It is measured according to the DMA test methods of IPC-TM-650 2.4.24 defineds.
(2) heat decomposition temperature：It is tested using TGA (Thermogravimetric Analysis), according to IPC-TM-650
2.4.24 the TGA test methods of defined are measured.
(3) peel strength：It is tested using anti-stripping instrument, according to the peel strength test of IPC-TM-650 2.4.24 defineds
Method is measured.
(4) Evaluation of Heat Tolerance：Using wicking method, will be placed in copper board samples in 288 DEG C of tin stoves, with 10 seconds for interval into
The cycle-index of layering blistering occurs for row test, record.
(5) the thermally stratified layer time：It is tested using TMA (Thermomechanical analysis), according to IPC-TM-650
2.4.24 the TMA test methods of defined are measured.
(6) punch forming：" S " type, observation molding situation are struck out with universal testing machine.
(7) flexure bending number：180 ° of flexure bending tests, note are carried out to copper-clad plate sample for bending radius with 2 millimeters
Number when record board samples are broken.
From test result as can be seen that the glass transition temperature (Tg) of the embodiment of the present invention, heat decomposition temperature (Td), stripping
It is got well than comparative example from intensity, heat resistance, flammability and punch forming, flexure bending etc..The phenol oxygen toughening of comparative example one
Epoxy resin, toughening while, are affected to Tg, heat resistance etc., and flexure bending is poor；Comparative example two phenol oxygen and block
Copolymer toughened epoxy, is susceptible to base material phenomenon of rupture during punch forming, and flexure bending is poor；Comparative example three
Epoxy resin toughened with activity poly ether sulfone and phenol oxygen, the punch forming effect of the copper-clad plate of making is bad, and flexure bending is poor；
Comparative example four is with activity poly ether sulfone and block copolymer come epoxy resin toughened, and the punch forming effect of the copper-clad plate of making is not
Good, flexure bending is poor；The dosage of six activity poly ether sulfone of comparative example five and comparative example is excessive or very few, cannot all obtain punching press
It is molded and bends the excellent semi-flexible copper-clad plate of bending；Hardener dose deficiency (with epoxy work as by amino equivalent in comparative example seven
Than being less than 0.5), the Tg of product declines amount, and heat resistance and flexure bending decline；Hardener dose is excessive in comparative example eight
(amino equivalent is more than 1.0 with epoxide equivalent ratio), the heat resistance and flexure bending of product are decreased obviously；It is embedding in comparative example nine
The 5% of the dosage deficiency epoxy resin of section copolymer, it is cracked in punching press to make copper-clad plate；Block copolymerization in comparative example ten
The dosage of object is more than the 40% of epoxy resin (and epoxy resin and toughened resin total amount), makes copper-clad plate heat resistance and stripping
Intensity declines.Comprehensive analysis carries out toughening to epoxy resin simultaneously using activity poly ether sulfone, phenol oxygen and block copolymer three
It is modified, composition glass transition temperature (Tg), heat decomposition temperature (Td), peel strength, flammability, heat resistance etc. can be improved,
There is humidification to toughness simultaneously；Made semi-flexible copper-clad plate punch forming and flexure bending is more preferable, and of the invention half
Flexibility coat copper plate can preferably meet static bending, 3 D stereo installation PCB requirements.
Above some preferred embodiments for only listing the present invention.Although the present invention illustrates this hair by above-described embodiment
Bright detailed composition, but the invention is not limited in above-mentioned detailed composition, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Composition could be implemented.Person of ordinary skill in the field is each to product of the present invention it will be clearly understood that any improvement in the present invention
The equivalence replacement of raw material and the addition of auxiliary element, the selection of concrete mode etc. all fall within protection scope of the present invention and openly
Within the scope of.
Claims (9)
1. a kind of resin combination, which is characterized in that the resin combination includes：Epoxy resin, the 20-100 of 100 parts by weight
The block copolymer of the activity poly ether sulfone of parts by weight, the phenoxy resin and 5-40 parts by weight of 5-80 parts by weight.
2. resin combination as described in claim 1, which is characterized in that the epoxy resin is bisphenol A type epoxy resin, contains
Phosphorus epoxy resin, biphenyl type epoxy resin, cycloaliphatic epoxy resin, without one or more of brominated eopxy resin combine.
3. resin combination as described in claim 1, which is characterized in that the activity poly ether sulfone has following structure：
Wherein, R1And R2Indicate active end group, R1And R2Can be identical or different, it is each independently selected from by hydroxyl, amido and alkene
The group of propyl composition；The integer that n is 5~500；
When the active terminal hydroxy group of the activity poly ether sulfone, the content range of reactive hydroxyl end group is 10-500 μ eq/g.
4. resin combination as described in claim 1, which is characterized in that the phenoxy resin has following structure：
Wherein, n=50~150, R1 and R2 can be identical or different, represent H atom, Br atoms each independently or contain P element
Group.
5. resin combination as described in claim 1, which is characterized in that the molecular weight of the block copolymer is 40,000-15
Ten thousand, for be selected from polymethyl methacrylate (PMMA), polybutadiene and polystyrene block structure unit triblock copolymer
Object.
6. resin combination as described in claim 1, which is characterized in that the resin combination also include curing agent and optionally
Curing accelerator.
7. resin combination as claimed in claim 6, which is characterized in that the curing agent is dicyandiamide, 4,4 '-diamino two
The combination of one or more of benzene sulfone, phosphorus-containing phenolic aldehyde, bisphenol-A phenolic, phenol type phenolic aldehyde, amino equivalent or hydroxyl equivalent and ring
The equivalent proportion of oxygen equivalent is 1:1~2；The curing accelerator is imidazoles curing accelerator.
8. a kind of copper-clad plate, which is characterized in that the copper-clad plate includes copper foil and the thermosetting resin that is attached on the copper foil
Composition impregnates base fabric, wherein the compositions of thermosetting resin is the thermosetting property according to any one of claim 1-7
Resin combination.
9. copper-clad plate as claimed in claim 8, which is characterized in that the copper foil be electrolytic copper foil or rolled copper foil, and/or,
The base fabric is glass fabric or non-woven fabrics.
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| CN201810413636.7A CN108727780B (en) | 2018-05-03 | 2018-05-03 | Resin composition and copper-clad plate manufactured by same |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810413636.7A CN108727780B (en) | 2018-05-03 | 2018-05-03 | Resin composition and copper-clad plate manufactured by same |
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| Publication Number | Publication Date |
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| CN108727780A true CN108727780A (en) | 2018-11-02 |
| CN108727780B CN108727780B (en) | 2021-08-27 |
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| CN201810413636.7A Active CN108727780B (en) | 2018-05-03 | 2018-05-03 | Resin composition and copper-clad plate manufactured by same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111748114A (en) * | 2020-05-14 | 2020-10-09 | 江阴市沪澄绝缘材料有限公司 | Epoxy glass cloth prepreg for oil gas exploitation bridge plug and production method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014043507A (en) * | 2012-08-27 | 2014-03-13 | Toray Ind Inc | Glass fiber fabric prepreg and glass fiber reinforced composite material |
| CN104487495A (en) * | 2012-07-25 | 2015-04-01 | 东丽株式会社 | Prepreg and carbon-fiber-reinforced composite material |
| CN107043520A (en) * | 2017-01-19 | 2017-08-15 | 景旺电子科技(龙川)有限公司 | A kind of composition epoxy resin of large aperture metal base printed circuit board consent and preparation method thereof |
| WO2018066600A1 (en) * | 2016-10-04 | 2018-04-12 | 三菱ケミカル株式会社 | Prepreg, prepreg laminate, and fiber-reinforced composite material |
-
2018
- 2018-05-03 CN CN201810413636.7A patent/CN108727780B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104487495A (en) * | 2012-07-25 | 2015-04-01 | 东丽株式会社 | Prepreg and carbon-fiber-reinforced composite material |
| JP2014043507A (en) * | 2012-08-27 | 2014-03-13 | Toray Ind Inc | Glass fiber fabric prepreg and glass fiber reinforced composite material |
| WO2018066600A1 (en) * | 2016-10-04 | 2018-04-12 | 三菱ケミカル株式会社 | Prepreg, prepreg laminate, and fiber-reinforced composite material |
| CN107043520A (en) * | 2017-01-19 | 2017-08-15 | 景旺电子科技(龙川)有限公司 | A kind of composition epoxy resin of large aperture metal base printed circuit board consent and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111748114A (en) * | 2020-05-14 | 2020-10-09 | 江阴市沪澄绝缘材料有限公司 | Epoxy glass cloth prepreg for oil gas exploitation bridge plug and production method thereof |
| CN111748114B (en) * | 2020-05-14 | 2022-04-12 | 江阴市沪澄绝缘材料有限公司 | Epoxy glass cloth prepreg for oil gas exploitation bridge plug and production method thereof |
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| Publication number | Publication date |
|---|---|
| CN108727780B (en) | 2021-08-27 |
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